Mechanisms of stereomutation and thermolysis of spiro-1,2-oxaphosphetanes: new insights into the second step of the Wittig reaction

J Am Chem Soc. 2012 Dec 5;134(48):19504-7. doi: 10.1021/ja307330c. Epub 2012 Nov 26.

Abstract

The experimentally observed stereomutation of spiro-1,2-oxaphosphetanes is shown by DFT calculations to proceed through successive M(B2) or M(B4) and M(B3) mechanisms involving two, four, and three Berry pseudorotations at phosphorus, respectively. Oxaphosphetane decomposition takes place in a single step via a polar transition state. The calculated activation parameters for this reaction are in good agreement with those determined experimentally.